Hybrid fuel and method of making the same

ABSTRACT

A hybrid fuel and methods of making the same. A process for making a hybrid fuel includes the steps of combining a biofuel emulsion blend and a liquid fuel product to form a hybrid fuel. Optionally, the hybrid fuel can be combined with water in a water-in-oil process and include oxygenate additives and additive packages. A hybrid fuel includes blends of biofuel emulsions and liquid fuel products, including light gas diesel. Optionally, the hybrid fuel can include water, oxygenate additives, and other additive packages.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit, and priority benefit, of U.S.Provisional Patent Application Ser. No. 61/794,115, filed Mar. 15, 2013,titled “Hybrid Fuel and Method of Making Same,” the disclosure of whichis incorporated herein in its entirety.

FIELD OF INVENTION

This invention generally relates to the formulation and production ofhybrid fuels, and, more specifically, to techniques for the productionof liquid fuels, including mineral-, plant-, and animal-basedhydrocarbons.

BACKGROUND

Transportable liquids are important commodities for fuel and chemicaluse. Currently, liquid hydrocarbons are mostly frequently produced fromcrude oil-based feedstocks by a variety of processes. However, as theworld supplies of crude oil feedstocks decrease, there is a growing needto find alternative sources of liquid energy products. Possiblealternate sources include biomass, coal and natural gas. Methane, whichis the major constituent of natural gas, biogas and coal gasification isa source along with emulsions including vegetable and animal fats. Worldreserves of natural gas are constantly being upgraded and more naturalgas is currently being discovered than oil.

Because of the problems associated with transportation of large volumesof natural gas, most of the natural gas produced along with oil,particularly at remote places, is flared and wasted. Hence theconversion of natural gas directly to higher hydrocarbons, is aparticularly attractive method of upgrading natural gas, providing theattendant technical difficulties can be overcome. A large majority ofthe processes for converting methane to liquid hydrocarbons involvefirst conversion of the methane to synthesis gas (“syngas” as usedherein), a blend of hydrogen and carbon monoxide. Production ofsynthesis gas is capital and energy intensive; therefore routes that donot require synthesis gas generation are preferred. For example,conventional hydrotreating utilizes two steps, first for production ofsyngas, and then creation of free radicals under high temperatures andpressure for reaction with oils to be hydrotreated. Such processes arevery energy intensive. A number of alternative processes have beenproposed for converting methane directly to higher hydrocarbons.

Existing proposals for the conversion of light gases such as methane andcarbon dioxide, as well as biofuels, to liquid fuels suffer from avariety of problems that have limited their commercial potential.Oxidative coupling methods generally involve highly exothermic andpotentially hazardous methane combustion reactions, frequently requireexpensive oxygen generation facilities, and produce large quantities ofenvironmentally sensitive carbon oxides. On the other hand, existingreductive coupling techniques frequently have low selectivity toaromatics and may require expensive co-feeds to improve conversionand/or aromatics selectivity. Moreover, any reductive coupling processgenerates large quantities of hydrogen and, for economic viability,requires a route for effective utilization of the hydrogen byproduct.Since natural gas fields are frequently at remote locations, effectivehydrogen utilization can present a substantial challenge.

Another key factor in hydrocarbon liquids is the presence of polynucleararomatic compounds, as well as total aromatic compounds. In someinstances, these compounds are known to be carcinogens. Regulatoryagencies have begun to turn their attention to the prevalence of thesecompounds in the environment and are requiring the reduction ofpolynuclear aromatics in industrial processes, including fuelprocessing. Moreover, polynuclear aromatics have a tendency to producefine particulates when they are combusted, leading to furtherenvironmental concerns. However, the reducing of polynuclear aromaticcompounds is difficult with existing refining processes because of thevariety, technical difficulty and expense of the different reactionpathways required for reduction of polynuclear aromatic compounds. Forexample, in certain situations, reduction of polynuclear aromaticcompounds requires addition of significant quantified of hydrogen gasand results in generation of carbon dioxide, which in itself requiresremoval and/or remediation.

A particular difficulty in using natural gas as a liquid hydrocarbonsource concerns the fact that many natural gas fields around the worldcontain large quantities, sometimes in excess of 50%, of carbon dioxide.Carbon dioxide is a target of increasing governmental regulation becauseof its potential contribution to global climate change. In addition, anyprocess that requires separation and disposal of large quantities ofcarbon dioxide from natural gas is likely to be economicallyprohibitive. In fact, some natural gas fields have such high carbondioxide levels as to be currently considered economically unrecoverable.

Similarly, the existing processes for the production of biofuels fromfats and oils commonly utilize esterification for the production ofBiodiesel, particularly in its unblended form (i.e., B100). This is acostly process, and there are known technical issues with utilizing theBiodiesel, particularly as B100, in existing installations. Embodimentsof the invention described below address these issues.

There are also large reserves of heavy oil/bitumen that cannot bereadily used. Economically reducing the viscosity (i.e., increasing theAPI gravity) of heavy oils increases their value to the refiner and alsoreduces the cost of transportation.

There is also a need to improve the performance of fuels fortransportation and heating applications. These improvements includeincreased efficiency for conversion of the energy to useful work andreduction of emissions of Greenhouse Gases (GHG), including CO₂,hydrocarbons, SOX, NOX, and of particulates. Further still, there isneed to reduce the aromatic fractions, including polycyclic aromatics,in hydrocarbon fuels and biofuels.

There is a need for an improved process for converting light gas (e.g.,methane) to liquid hydrocarbons, particularly where the light gas ispresent in a natural gas stream containing large quantities of carbondioxide. There is also a need to create a hybrid fuel to utilize theunique characteristics of products produced from natural gas, bio fatsand oils, crude and heavy oil/bitumen in a blended fuel that can beproduced at costs comparable with existing hydrocarbon fuels. There is aneed for process integration, systems, and apparatus that reduce thetotal emissions of Greenhouse Gases (GHG) and particulates based on LifeCycle analysis. Such processes also require the potential to utilizecarbon dioxide to minimize the emissions thereof.

BRIEF SUMMARY OF THE INVENTION

The invention provides hybrid fuels and methods for making the same.

In one aspect, a hybrid fuel is disclosed that is prepared from aprocess that includes: introducing a first reactant to a reactor, wherethe first reactant includes one or more light gases; exposing the firstreactant to non-thermal plasma under conditions sufficient to reform thefirst reactant to form syngas and to generate free radicals andenergetic electrons; introducing a first liquid feed fuel to thereactor; and intimately contacting the reaction products from theexposure of the first reactant to non-thermal plasma with the firstliquid feed fuel in the reactor to produce a modified liquid fuel. Asdisclosed herein, the hybrid fuel prepared in accordance with thedisclosed processes is usable as a drop-in fuel. In certain embodiments,a blend or mixture is prepared with the hybrid fuels prepared inaccordance with the invention. Such blends include, without limitation,biodiesel, biofuel emulsions, jet fuel, diesel, and other conventionalfuel products as the other components to the mixture. In one embodiment,the first reactant further comprises a second liquid fuel feed.

In one aspect a hybrid fuel is provide the hybrid fuel includes a firstfuel product and a second fuel product. The first fuel product includes,without limitation a biofuel emulsion, biodiesel, jet fuel, diesel,ultra-low-sulfur diesel or other petroleum based fuels (e.g., the resultof 102 of FIG. 1 or 222 of FIG. 2). The second fuel product includes afuel prepared from one or more light gases combined with a liquid fuelfeed (e.g., 328 of FIG. 3B or the result of 104 of FIG. 11. In someembodiments, the hybrid fuel includes at least about 20% by weight ofthe first fuel product. In some embodiments, the hybrid fuel includes upto about 20% by weight of the first fuel product. In furtherembodiments, the hybrid fuel includes from about 5% to about 10% byweight of the first fuel product. In other embodiments, the hybrid fuelincludes water. In some embodiments, the hybrid fuel includes about 20%by weight of the first fuel product and about 80% by weight of thesecond fuel product. In some embodiments the hybrid fuel furtherincludes up to about 20%, or about 10% to about 20% or about 20% water,the balance of the composition including the second fuel product. Insome embodiments, the pour point of the hybrid fuel is about −30° C. Inother embodiments, the pour point of the hybrid fuel is less than about−15° C. In further embodiments, the pour point of the hybrid fuel isabout −10° C. to about −50° C., or about −25° C. to about −35° C. Inother embodiments, the cloud point of the hybrid fuel is about −44° C.In further embodiments, the cloud point of the hybrid fuel is no morethan about −10° C., or is about −15° C. In some embodiments, the pourpoint of the hybrid fuel is about −10° C. to about −15° C., or about 15°C. lower than the pour point of the second fuel product in isolation(i.e., not in the presence of the first fuel product, or prior tocombining to produce the hybrid fuel). In some embodiments, the hybridfuel includes no more than about 1% polynuclear aromatics. In otherembodiments, the hybrid fuel includes no more than about 20% aromatics.In some embodiments, the second fuel product is a hybrid fuel producedfrom the processes described herein. In some embodiments, the first fuelproduct also includes a glycerol ether.

In another aspect, a process for the preparation of a hybrid fuel isdisclosed. The process includes: introducing a first reactant to areactor, where the first reactant includes one or more light gases;exposing the first reactant to non-thermal plasma under conditionssufficient to generate syngas (i.e., CO+H₂) and free radicals;introducing a first liquid feed fuel to the reactor; and intimatelycontacting the synthetic gas and the free radicals generated from thefirst reactant with the first liquid feed fuel in the reactor to producea modified liquid fuel. In some embodiments, the hybrid fuel is abiofuel. In some embodiments, the process is a process for the refiningof oil. In some embodiments, the process of generating free radicals isnot preceded by a process for disassociating the one or more light gases(i.e., the reaction products from the first reactant are directlyintermingled with the first liquid feed fuel). In some embodiments, thereactor is a non-thermal plasma reactor. In some embodiments, thenon-thermal plasma reactor is a gliding arc reactor, a micro-plasmagenerator, or a homogenizer. In some embodiments, the free radicals aregenerated by high shear, ultrasonic, cavitation, high energy mixingdevices, or combinations thereof.

In some embodiments, the processes for preparing a hybrid fuel disclosedherein further include adding a catalyst in the reactor. In someembodiments, the catalyst is a metal catalyst, an organometalliccatalyst, a nanosphere catalyst, a supported catalyst, a solublecatalyst, or a mixture of two or more. In some embodiments, the catalystis an organomolybdenum compound.

In some embodiments, the processes for preparing a hybrid fuel disclosedherein forms fatty acid ethyl esters (FAEE) and glycerol as byproducts.In some embodiments, the glycerol byproduct is further reacted to formone or more glycerol ether products, which is added to the hybrid fuel.

In a further aspect, a process for reforming light gas is provided. Theprocess includes reforming one or more light gases in the presence ofnon-thermal plasma under conditions sufficient to generate the formationof free radicals. In certain embodiments, the reforming step is one ormore of dry reforming (i.e., reacting methane with carbon dioxide in areactor such as a plasma reactor), steam reforming, partial oxidation,and formation of methyl radicals. In some embodiments, the step ofreforming one or more light gases is preformed at a pressure of lessthan about 5 atm. In other embodiments, the process is conducted at atemperature from about 200° C. to about 500° C. In some embodiments, thereforming step is one or more of dry reforming, steam reforming, partialoxidation, and formation of methyl radicals.

In some embodiments, in the processes for preparing a hybrid fueldisclosed herein the light gas is methane, natural gas, or a mixturethereof.

In one aspect, an apparatus for the preparation of a hybrid fuel isdisclosed. The apparatus includes a first inlet for introducing a firstreactant, where the first reactant comprises one or more light gases;electrodes in fluid connection with the inlet, where the electrodes arecapable of producing an arc upon application of voltage and wherein theelectrodes define a path for passage of the first reactant; a secondinlet for introducing a first liquid feed fuel to the apparatus; an exitzone in which the product of the reaction of the first reactant and theelectrodes and the first liquid feed fuel comes into contact; and anoutlet in fluid connection with the exit zone. In some embodiments, theexit zone is interposed between and in fluid communication with the pathdefined by the electrodes and the second inlet. In some embodiments, theapparatus also includes Helmholtz coils. In some embodiments, theHelmholtz coils are located in or near the reactor. In some embodiments,the Helmholtz coils are located in or near the exit zone.

In some embodiments, the apparatus further includes a catalyst. In someembodiments the catalyst is located in or near the exit zone.

In some embodiments, the apparatus further includes heating coils. Insome embodiments, the heating coils are capable of heating the contentsof the apparatus to a specified temperature.

In some embodiments, the apparatus further includes a low work forcecathode. In some embodiments, the low work force cathode functions toincrease electron flow and/or electron density. In some embodiments, thelow work force cathode includes thorium.

In one aspect, a process for the conversion of light gases into liquidsis provided. Exemplary processes are those that utilize the generationof free radicals for the conversion process. In some nonlimitingembodiments, the processes include utilizing non-thermal plasma.Non-thermal plasma is utilized to reform the light gases, i.e., toproduce syngas (H₂ and CO), radicals, energetic electrons, or a mixtureof two or more of these components. In certain embodiments, reactiveintermediates generated in the plasma are converted directly to producemolecules of hydrocarbon fuels. Such embodiments provide for rapidtransfer of exiting gases into liquid fuel feed, such as diesel or othersuitable hydrocarbon liquid. Particular embodiments take advantage ofthe presence of the free radicals, which are short lived, and reactsthem with a liquid fuel feed (e.g., in some embodiments, oil or a bioliquid) to hydrogenate the compounds present in the liquid fuel feed,thereby forming shorter chain molecules. In certain embodiments,utilizing a non-thermal plasma reactor has the advantage of maximizingthe electron density in the reaction space.

In certain embodiments, the processes disclosed herein result in areduction in the content of polynuclear aromatics and total aromatics inthe hybrid fuel. For example, in some embodiments, the processesdisclosed herein result in a concentration of polyaromatic compounds ofless than about 5%, less than about 3%, less than about 2%, or less thanabout 1%, less than about 0.1% by weight. In some embodiments, theprocesses disclosed herein result in a concentration of aromaticcompounds of less than about 35%, less than about 30%, less than about25%, or less than about 20% by weight. In some embodiments, theprocesses disclosed herein result in a at least a two-fold, three-fold,five-fold, or ten-fold reduction in polyaromatic compounds relative toconventional processes. Additionally, the processes disclosed hereinresult in an increased volume of fuel product, relative to conventionalfuel processes. Accordingly, the processes disclosed herein modify themolecular makeup of the components, resulting in a hybrid fuel that isrelatively cleaner burning and having lower emissions of greenhousegases and small particle smoke. Moreover, the processes disclosed hereresult in fuels with lower viscosity and pour points.

In the embodiments disclosed herein, the light gas includes, withoutlimitation, methane, ethane, butane, CO₂, H₂O, and H₂S.

In certain embodiments, the biogas used in the processes disclosedherein contains up to about 40% CO₂. In some embodiments, the processesare useful for the treatment of heavy oils (e.g., sour crude) to lowerthe viscosity. The end products of the processes disclosed hereininclude heating oil, diesel, gasoline (petrol), marine and jet fuels.

In another aspect, processes for the reforming of methane and otherlower hydrocarbons via the use of free radicals are disclosed. In someembodiments, the reforming processes have the advantage of producingreaction products that contain relatively low levels of aromaticcompounds and polynuclear aromatic compounds. In particular embodiments,the processes disclosed herein result in a reduction in the formation ofaromatic compounds and polynuclear aromatic compounds relative toconventional processes. In some nonlimiting embodiments, free radicalgeneration is achieved through the use of non-thermal plasma.

In one aspect of the invention, a process for making a hybrid fuel isdisclosed. The method includes the steps of combining a biofuel emulsionblend and a liquid fuel product to form a hybrid fuel. Optionally, thehybrid fuel can be combined with water in a water-in-oil process. Stillfurther, and optionally, the hybrid fuel can be combined with oxygenateadditives and additive packages.

In another aspect of the invention, a process for making a biofuelemulsion includes combining an oil and an alcohol, and, optionally, anemulsifier. The mixture is subjected to high pressure and then passed toan expansion chamber, which homogenizes the mixture. The mixture is thenat least partially oxidized to produce a biofuel emulsion.

In a further aspect of the invention, a process for making a liquid fuelproduct includes combining a light gas and a liquid fuel feed, and,optionally, water, a catalyst, and an emulsifier into a mixture. Themixture is reacted in a reactor vessel to produce at least one modifiedfuel product in vapor form. The method can, optionally, include reactingthe modified fuel vapor product in a gas phase catalytic reactor andcondensing the vaporous product into a liquid fuel product.

In another aspect of the invention, a hybrid fuel is disclosed.Embodiments of the hybrid fuel include blends of biofuel emulsions andliquid fuel products. Implementations of the hybrid fuel can also becombined with water, oxygenate additive, and other additive packages.

In one aspect, the process described herein forms free-radicals as aresult to supercritical homogenizer reaction, thus forming Fatty AcidEthyl Esters (FAEE) and glycerol similar the products formed viaconventional biodiesel processes. The glycerol can be removed andprocessed to ethers of glycerol, the ethers of glycerol can then beadded to emulsion to lower the pour point and reduce the viscosity ofthe product.

Without wishing to be bound by a particular theory, it is speculatedthat the processes described herein for preparing hybrid fuels,including biofuels, are energy favorable. Moreover, test results havedemonstrated an overall decrease in density of the hybrid fuel mixture,providing confirmatory evidence that the overall beneficialhydrogenation of aromatic compounds to hydrocarbons is occurring (i.e.,the process successfully converts otherwise undesirable aromatics touseful fuel stock).

In one aspect, a process for producing feedstock is disclosed. Theprocess includes: supplying carbonaceous feedstock to a hydromethanationreactor; and reacting the carbonaceous feedstock in the presence of acatalyst and steam to produce a plurality of gases. In some embodiments,the carbonaceous feedstock is coal, biomass, petroleum coke, or amixture thereof. In some embodiments, the catalyst is an alkali metal.In some embodiments, the reacting step is performed under elevatedtemperature, pressure, or both.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

For a more complete understanding of various embodiments of the presentinvention, reference is now made to the following descriptions taken inconnection with the accompanying drawings in which:

FIG. 1 illustrates an integrated process for producing a hybrid fuelaccording to one embodiment of the invention.

FIG. 2 illustrates a process for producing a biofuel emulsion accordingto one embodiment of the invention.

FIG. 3A illustrates a process for producing a liquid fuel productaccording to one embodiment of the invention.

FIG. 3B illustrates a process for producing a liquid fuel productaccording to one embodiment of the invention.

FIG. 4 illustrates a further process for producing a hybrid fuelaccording to one embodiment of the invention.

FIG. 5 illustrates a process for producing a water and oil blend productaccording to one embodiment of the invention.

FIG. 6 illustrates an additive package mixing process.

FIG. 7 illustrates a process for producing hybrid fuel feedstocks fromheavy oils according to one embodiment of the invention.

FIG. 8 illustrates a further process for producing hybrid fuelfeedstocks from carbonaceous materials according to one embodiment ofthe invention.

FIG. 9A illustrates a reactor configuration for producing a liquid fuelproduct according to one embodiment of the invention.

FIG. 9B illustrates a reactor configuration for producing a liquid fuelproduct according to one embodiment of the invention.

FIG. 9C illustrates a reactor configuration for producing a liquid fuelproduct according to one embodiment of the invention.

FIG. 9D illustrates a reactor configuration for producing a liquid fuelproduct according to one embodiment of the invention.

DETAILED DESCRIPTION

The term “biogas” is used herein to include any non-inert gas that canbe produced by the biological degradation of organic matter.Non-limiting examples of biogas are hydrogen, methane, and carbonmonoxide. Biogases, as used herein, also include other gaseouspetroleum-based products such as ethane and ethylene, as well asdecomposition products of agricultural waste such as wood chips, grains,grasses, leaves, and the like. The term “biogas” is also used herein toinclude the same gases that are obtained from other sources. One exampleis methane associated with coal, commonly known as “coal bed methane,”“coal mine methane,” and “abandoned mine methane.” In some embodiments,such methane is derived by bacterial activity or by heating.

The term “natural gas”, as used herein, is intended to mean a collectionof materials that is formed primarily of methane, but it can alsoinclude ethane, propane, butane and pentane. The composition of naturalgas can vary widely (e.g., varying from about 70%-100% or about 70% toabout 90% methane, about 5%-15% ethane, and up to about 5% or up toabout 20% propane or butane, individually or together), and it caninclude carbon dioxide, oxygen, water, nitrogen, hydrogen sulfide, anrare gases (e.g., argon, helium, neon, and xenon).

The term “light gas”, as used herein, is intended to mean gasesincluding carbon dioxide and hydrocarbons containing at least twocarbons, such as methane, ethane, propane, ethanol, methanol, andmixtures of two or more thereof. In some embodiments, water is alsoincluded.

The term “biofuel”, as used herein, generally refers to a liquid fuelthat is made from animal, plant, and/or biological materials.

Under one aspect of the invention, hybrid fuels and methods of makingthe same are disclosed. The term “hybrid fuels”, as used herein,generally refers to any one of many possible fuel formulations orblends, including “drop-in” fuel formations that use any one or more ofreadily available light gases (described in more detail below),hydrocarbon fractions, biofuels, water, and various additive packages.In some embodiments, hybrid fuels include the fuel product resultingfrom the combination of a light gas and a liquid fuel feed (e.g.,natural gas and diesel). A drop-in fuel is one that is interchangeableand compatible with the conventional fuel it replaces. A drop-in fueldoes not require adaptation of the heating system, burner system, engineor jet fuel system or modification of the fuel distribution network inwhich it is used. A drop-in fuel can be used “as is” or can be blendedwith the conventional fuel the drop-in fuel replaces.

“Energetic electrons” as used herein refer to electrons having elevatedelectron energy, such that they are able to participate in thedecomposition of gaseous molecules (e.g., decomposition of methane ornatural gas by disassociation or ionization). Energetic electrons arepart of the processes disclosed herein (including without limitation theuse of nonthermal plasma) that enable otherwise thermodynamicallyunfavorable reactions to occur. In some nonlimiting embodiments,energetic electrons have electron energy of about 1-10 eV, or greaterthan about 5 eV, or great than about 6.5 eV or even greater than about10 eV. In some embodiments, a sufficient number of energetic electrons,or high-energy electrons, are involved with a phenomenon called electronavalanche, wherein secondary electrons are generated. In certainsituations, the fragmentation pattern on radicals formed from methane isdependent in part of the electron energy distribution function (EEDF).

Embodiments of the processes for making hybrid fuels are flexible, fullyintegrated, and can be readily adapted to the available feedstockson-hand as well as adapted to the type of hybrid fuel desired. Forexample, embodiments of the process can be adapted to produce drop-inreplacements for any one or more of heating oil, diesel, gasoline,marine fuel, and jet fuel (e.g., Jet A, JP-8, JP-5, etc.). Similarly,embodiments of the process can be adapted to accept varying feedstocks,such as, plant oils, animal-derived fats, alcohols, natural gas, CO₂,heavy oils, diesel, biodiesel, and products from the gasification ofbiomass, coal, coke, and other materials. The integrated processesdisclosed herein provide flexible operations that maximize economics offuel availability and meet the requirements of multiple fuel usesincluding heating, transportation (e.g., vehicle, marine, jet, etc.)requirements. The processes disclosed herein are applicable to a largenumber of locations, including remote locations with limited natural gasreserves, and are suitable for moving equipment by truck or barge.Moreover, the processes have relatively low utility consumption (e.g.,water) and involve relatively lower capital cost to implement.

As mentioned above and described in greater detail below, embodiments ofthe invention provide highly integrated processes for the production ofhybrid fuels. A highly integrated plant is less sensitive to feedstockprice and availability because many of the feedstocks for the individualprocesses are “internally supplied”. That is, the primary orside-products of one sub-process feed the other sub-processes. Thus, afewer number of feedstocks must be brought in from outside the process,which reduces the overall exposure to feedstock supply volatility.

Furthermore, the performance of the overall process is enhanced by ahigh degree of process integration. The flexibility of a highlyintegrated process enables the order of processing of the sub-processesto be changed to accommodate available feedstocks and desired hybridfuel products. Similarly, the process can adapt to changing productdemand and product economics by accommodating the manufacture ofalternate hybrid fuel products. Environmental performance, too, isenhanced because by-products of certain sub-processes that wouldotherwise require disposal can be used as feedstocks for othersub-processes. This also reduces the costs of operation because disposalcosts are avoided as well as the cost of the feedstocks themselves.Further still, in many cases, the capital expenditure for the entireintegrated plant is lower than what would be incurred if the individualsub-processes were built independently. Likewise, transportation coststhat would be incurred by shipping materials from one sub-process toanother are avoided in an integrated process.

In one aspect, the processes disclosed herein include the formation offree radicals from light gases and utilizing the free-radicals insubsequent processes for the production of hybrid fuels. The processesdisclosed herein demonstrate an advantage over conventional processesthat require two distinct steps—a first step of disassociating a lightgas and a second, subsequent step, of again creating free radicals athigh temperatures and pressures to initiate further processing steps.The processes disclosed herein limit the need for these two distinctsteps, thereby providing significant advantages (such as lower energyconsumption) to the refiner and user. In exemplary embodiments disclosedherein, free radicals generated in the initial step are directlyutilized in processes for the refining of oil and other fuel feedliquids. Moreover, the free radicals are available for use in otherprocesses. The processes disclosed herein incorporate intimate (i.e.,near term) contact with free radicals of the vapor phase and thesubsequent liquid fuel feed (e.g., liquid or oil liquid phase) withinthe time of the existence of the free radical.

In another aspect, free radicals containing carbon, hydrogen, oxygen, ora mixture of two or more of carbon, hydrogen, and oxygen are created inprocesses for the reforming of light gases. In some embodiments, thereforming process is dry reforming (CO₂+CH₄), steam reforming, partialoxidation, or the formation of methyl radicals. In some embodiments, theprocess of reforming light gases is conducted in the presence ofnon-thermal (non-equilibrium) plasma. In some embodiments, the processof reforming light gases using non-thermal plasma is conducted atatmospheric pressure. In other embodiments, the process of reforminglight gases using non-thermal plasma is conducted above atmosphericpressure. For example, in some embodiments, the process is performed ata pressure ranging from about 0.1 atm to about 5 atm. In someembodiments, the process is performed at a pressure up to about 5 atm.In some embodiments, the process is performed at pressure of about 100Torr. In other embodiments, the reforming process is conducted underhigh shear conditions caused by ultrasonic excitation, spinning disks,homogenization, UV light sources, radiation, or a combination of two ormore of these processes. In some embodiments, the radiation is electronradiation or particle (gamma) radiation or a combination thereof. In oneembodiment, the source of radiation is thorium.

In conventional high temperature-high pressure processes, free radicalsare formed during the reforming process, The claim is that the freeradicals can be formed using a non-thermal (non-equilibrium) plasma. Theenergy consumption is lower. In a similar manner, the subsequent hydroprocessing of the liquids occurring at high temperature results in theformation of free radicals leading to chain reactions. The claim is thatbringing the syngas with free radicals back to neutral and thenrecreating the free radical state is energy inefficient. The processutilizes the free radicals formed during the plasma operation to causethe continuing chain reactions. Similarly, the processes using thenoon-thermal reactor likewise return the syngas or methyl radical backto normal condition.

In some embodiments, the processes disclosed herein include the use ofcatalysts. Such catalysts facilitate the gas shift reaction, as well asthe rearrangement of the hydrocarbons. Exemplary catalysts include,without limitation, metals, nanospheres, wires, supported catalysts, andsoluble catalysts. For example, as used herein, “nanosphere” or“nanocatalyst” refers to a catalyst in which the mean average diameterof the catalyst is in the range of 1 nm to 1 μm. In some embodiments,the catalyst is an oil soluble catalyst (also known as nanocatalysts).Such catalysts disperse well and do not precipitate during oilprocessing. In some embodiments, the catalysts is a bifunctionalcatalyst, for example one that includes an inorganic base and a catalystcontaining a transition metal such as iron, chromium, molybdenum, orcobalt. In certain embodiments, catalysts are present in the reactionprocess at levels of about 0.03% to about 15% by weight. In someembodiments, the catalyst is present at a level of about 1%. In onenonlimiting exemplary embodiment, the concentration of soluble catalystintroduced into the reactant mixture falls is about 50 ppm, or about 100ppm, or ranging from about 50 ppm to about 100 ppm of liquid oil. Insome embodiments, the catalyst is present at a level of at least about50 ppm. In some embodiments, the catalyst is present at a level rangingfrom about 50 ppm to about 100 ppm. In some embodiments, the catalyst ispresent at a level ranging.

In some embodiments, the catalyst is an organometallic compound.Exemplary organometallic compounds contain a transition metalatransition metal-containing compound, or mixtures thereof. Exemplarytransition metals included in catalyst compounds include catalystsselected from the Group V, VI and VIII elements in the Periodic Table ofElements. In certain embodiments, the transition metal of the catalystsis one or more of vanadium, molybdenum, iron, cobalt, nickel, aluminum,chromium, tungsten, manganese. In some embodiments, the catalyst is ametal naphthanate, an ethyl sulfate, or an ammonium salt of polymetalanions. In one embodiment, the catalyst is an organomolybdenum complex(e.g., MOLYVAWM 855 (R.T. Vanderbilt Company, Inc. of Norwalk, Conn.,CAS Reg. No. 64742-52-5), an organomolybdenum complex of organic amidecontaining about 7% to about 15% molybdenum. In another embodiment, thecatalysts is HEXCEM (Mooney Chemicals, Inc., Cleveland, Ohio, containingabout 15% molybdenum 2-ethylhexanote) or bimetallic wire, shavings orpowder catalyst that is H25/L605 (Altemp Alloys, Orange Calif.) thatincludes about 50-51% cobalt, 20% chromium, about 15% tungsten, about10% nickel, up to about 3% iron, and 1.5% manganese.

In further embodiments, other suitable catalysts include compounds thatthat are highly soluble in oil while having a relatively high loading ofmolybdenum. In some embodiments, the catalyst imparts lubricity to thefuel, which is necessary for ultra-low-sulfur diesel products (ULSDs),which. In some embodiments, the organometallic compound adds lubricityto the liquid fuel product, as well as serving as a catalyst, therebyavoiding the need to add further lubricity additives to the final hybridfuel product. Other organometallic compounds that are useful for theprocesses disclosed herein are those disclosed in U.S. Pat. No.7,790,018 to Khan, et al. and U.S. Pat. No. 4,248,720 to Coupland et al.

In some embodiments, the transition metal catalyst is a singletransition metal or a combination of transition metals, either as metalsalts, pure metals, or metal alloys, and, in some embodiments is used incombination with metals other than transition metals. Preferredcatalysts for use in this invention are metals and metal alloys. In someembodiments, transition metals having atomic numbers ranging from 23 to79 are employed; in other embodiments, those with atomic numbers rangingfrom 24 to 74 are more employed. In some embodiments, cobalt, nickel,tungsten, iron, and combinations thereof are employed as metals forcatalyst compounds. A nonlimiting example of an additional metal thatcan be included is aluminum. In some embodiments, the transitionmetal(s), together with other metals such as aluminum are supported aniron frame. In some embodiments, the metal frame is a basket or in abed. In some embodiments, the catalyst is deposited onto the surface ofthe electrode. A variety of forms of iron can be used as the framematerial. Nonlimiting examples are pig iron, gray iron, and ductileiron. In certain embodiments, the metal windings are supported on theiron frame in the form of an open-mesh network, For example, in someembodiments. Gray iron castings include, for example, total carbon, 2.75to 4.00 percent; silicon, 0.75 to 3.00 percent; manganese, 0.25 to 1.50percent; sulfur, 0.02 to 0.20 percent; and phosphorus, 0.02 to 0.75percent. Moreover, in some embodiments, one or more of the followingalloying elements are present in varying amounts: molybdenum, copper,nickel, vanadium, titanium, tin, antimony, and chromium. In someembodiments, nitrogen is generally present in the range of about 20 toabout 92 ppm.

The rate and extent of chemical reactions are limited by the laws ofkinetics and thermodynamics. The rate of reaction is dependent on manythings, including time, temperature, and pressure. In the case ofcatalyzed reactions there is the additional rate limiting factor of thecontact time of the reactants with the catalyst and the time for reactedproducts to be removed from the surface of the catalyst to enable thecatalyst to catalyze further reactants.

In some embodiments, the process to combine light gas with a liquid fuelfeed is operated at temperatures from about 100° C. to about 850° C. Insome embodiments, the process is performed at room temperature. In someembodiments, the process is performed at temperatures from about 200° C.to about 500° C., or about 500° C. to about 700° C. or about 700° C. to850° C. In other embodiments, the process is performed at temperaturesfrom about 300° C. to about 500° C. In some embodiments, the gases andliquid fuel feed are heated. The temperature is controlled to assist inthe reaction process.

In some embodiments, the process is performed at pressure above 1 atm.In some embodiments, the process is performed at atmospheric pressure.In certain embodiments, the process is performed at positive pressureranging from about 0.1 atm to about 5 atm. In some embodiments, theprocess is performed at pressure of no more than about 5 atm. In certainembodiments (e.g., microplasma reactors), the process is performed atpressures of up to about 100 Torr. In some embodiments, the pressureranges from about 1200 psi to about 3000 psi.

In some embodiments, the process for producing a biofuel from acombination of a light gas and a liquid fuel feed is a liquid/gas or avapor/gas phase process.

In some embodiments, the apparatus for reforming natural gas or forproducing a biofuel is a non-thermal plasma reactor. Nonlimitingexamples of non-thermal plasma reactors include gliding arc, vortex arc,distributed discharge, micro channel discharge, and dielectric barrier.In some embodiments, the apparatus or reactor includes a radiationsource. Exemplary radiation sources include, without limitation,thorium. In some embodiments, the apparatus or reactor includes low workforce materials to increase electron flow. In some embodiments, theapparatus or reactor includes a magnetic field.

The apparatus for producing free radicals includes, without limitation,non-thermal plasma reactors, high shear reactors, electron or particlebeam reactors, and hybrid systems. Non-thermal plasma reactors includethose in which electrons are activated and free radicals form underrelatively low temperature conditions. In some embodiments, non-thermalplasma reactors utilize and external electrical source to createelectric fields. The applied voltage is, in some embodiments, DC, whilein other embodiments it is high frequency. Exemplary non-thermal plasmareactors include, without limitation, Gliding Arc reactors, microplasmareactors, homogenizers, high shear reactors. In further nonlimitingembodiments, non-thermal plasma reactors include vortex generators,micro-plasma generators, rotating disk with centrifugation, highfrequency, microwave, and sonic activation. Nonlimiting examples of highshear reactors are homogenizer reactors, ultrasonic reactors, cavitationreactors, high energy mixing devices, and catalytic centrifugationreactors. Exemplary electron or particle beam free radical generatorsinclude, without limitation, high energy electron generators andradioactive sources. For example, in one embodiment, the radioactivesource is a material that generates alpha particles, such as thorium.

In some embodiments, the reactors are microplasma reactors. Microplasmasare plasma reactors in sub-millimeter geometry. They possess highelectron densities and a relatively high fraction of energetic (>20 eV)electrons which are theoretically able to efficiently promote chemicalreactions. The microplasma reactors utilized herein operate with anonthermal plasma and are ignited using either a direct current orpulsed DC power supply (<80 kHz). In one particular embodiment, thedevice is a microhollow cathode discharge (MHCD) with an elongatedtrench.

The use of microplasma technology to create the radicals from thereforming of natural gas provides higher electron and free radicaldensities, which should theoretically increase the overall efficiency.Plasma confined to at least one dimension 1 mm or less defines amicroplasma. Microplasmas have much higher power densities (exceeding 1kW/cm³), higher electron densities (exceeding 10¹⁵ cm⁻³) and increasedsurface-to-volume ratios when compared to conventional, large-scaleplasma-chemical systems. A high surface-to-volume ratio impartsexcellent thermal management and mixing characteristics that helpmaintain homogeneous, isothermal reacting volumes. These microplasmacharacteristics present processing advantages for hydrocarbon reformingapplications. Operating at close to atmospheric pressure minimizesequipment requirements and simplifies the overall operating system.

In conventional reactors, contact time for the reactants and catalyst isoften controlled by mixing which provides contact between componentsinvolved in a chemical reaction. There have been various innovationsdirected towards maximizing the use of mixing and mixing devices toaccelerate chemical reactions. High shear and high energy mixing deviceshave been proposed for enhancing the rate of chemical reactions. Therehave been other devices proposed for accelerating the reactions ofchemical reactants. For example, hydrodynamic cavitation has beenproposed as a method of accelerating chemical reactions. Hydrodynamiccavitation involves phase change and rapid increases in temperatures andpressures; pressure variation caused by the variation in the flowingliquid velocity results in accelerated chemical reaction.

In general, a high shear reactor is also referred to as an emulsifiermixer, dispersion mixer, or sonic unit. Implementation of a specificreactor and process will include consideration of, among other things,the scale, cost, quality and quantity of feedstock. Homogenizer reactorsare one type of configuration useful for the processes disclosed herein.

Without wishing to be limited to a particular theory, it is believedthat the level or degree of high shear mixing is sufficient to increaserates of mass transfer and may produce localized, non-ideal conditionsthat enable reactions to occur that would not otherwise be expected tooccur based on Gibbs free energy predictions. Localized, non-idealconditions are believed to occur within the high shear device resultingin increased temperatures and pressures with the most significantincrease believed to be in localized pressures. The increase inpressures and temperatures within the high shear device areinstantaneous and localized and quickly revert to bulk or average systemconditions once exiting the high shear device. In some cases, the highshear-mixing device induces cavitations of sufficient intensity todissociate one or more of the reactants into free radicals, which mayintensify a chemical reaction or allow a reaction to take place at lessstringent conditions than might otherwise be required. Cavitation mayalso increase rates of transport processes by producing local turbulenceand liquid microcirculation (acoustic streaming). An overview of theapplication of the cavitation phenomenon in chemical/physical processingapplications is provided by Gogate et a!., “Cavitation: A technology onthe horizon,” Current Science 91 (No. 1): 35-46 (2006). The high shearmixing device of certain embodiments of the present system and methodsis operated under what are believed to be cavitation conditionseffective to dissociate the reactants for the optimization of reactions.In certain instances, the conditions are effective for mechanicallydisintegrating and/or extracting hydrocarbons. Further, the conditionsmay be effective for mechanically homogenizing the hydrocarbon chains toproduce liquid hydrocarbon products.

In some embodiment, tip speed, and therefore shear rate, is an importantfactor in achieving fine micro-emulsions. In one particular embodiment,SUPER DISPAX REACTOR combines extremely high shear rates with a finegenerator geometry to produce high energy dispersions. Due to the hightip speeds, two stages are often all that is needed to achieve theresults that are desired. In some embodiments, tip speeds exceeding10,000 fpm are achieved.

High shear devices (HSD) such as high shear mixers and high shear mills,are generally divided into classes based upon their ability to mixfluids. Mixing is the process of reducing the size of in homogeneousspecies or particles within the fluid. One metric for the degree orthoroughness of mixing is the energy density per unit volume that themixing device generates to disrupt the fluid. The classes aredistinguished based on delivered energy density. There are three classesof industrial mixers having sufficient energy density to consistentlyproduce mixtures or emulsions with particle or bubble sizes in the rangeof 0 to 50 flm.

Homogenization valve systems are typically classified as high-energydevices. Fluid to be processed is pumped under very high pressurethrough a narrow-gap valve into a lower pressure environment. Thepressure gradients across the valve and the resulting turbulence andcavitations act to break-up any particles in the fluid. In someembodiments, these valve systems yield average particle size range fromabout 0.01 flm to about 1 flm. At the other end of the spectrum are highshear mixer systems classified as low energy devices. These systemsusually have paddles or fluid rotors that turn at high speed in areservoir of fluid to be processed, which in many of the more commonapplications is a food product. These systems are usually used whenaverage particle, globule, or bubble, sizes of greater than 20 micronsare acceptable in the processed fluid.

In some embodiments of non-thermal plasma reactors, a heterogeneousmedium of the heavy hydrocarbon with a hydrogen-containing gas (e.g.,syngas) in a chamber is exposed to both an electronic beam and anelectric discharge field at the same time so as to create a thermalnon-equilibrium as well as a spatially non-uniform state for thismedium. Such dual exposure allows the cracking method to proceed withouthigh temperature and high pressure typically required therefore and thusreduces the energy consumption and impurities generated along withdesirable output product.

In other embodiments, a non-self sustaining electric discharge occurs byan external ionizer of a very high intensity, such as an Electron Beam(EB). An electric field of high intensity superimposed on the gas that,in turn, is exposed to the EB multiplies a number of electrons generateddue to EB, and creates an electric discharge, which generates chemicallyactive particles. Numerous applications of these discharges inhomogeneous media are well known (e.g., for activating gas lasers). Forexample, chemical activity of an electric discharge supported by EB in ahomogeneous gas is described in Y N Novoselov, V V Ryzhov, A ISuslov//Letters in Journal of Theoretical Physics, 1998. v. 24. No. 19;p. 41.

Similarly, the injection of gamma rays into the non-thermal plasma zonecontaining the gases causes is believed to improve the stability of theplasma and facilitate the initiation of the formation of free radicals.The 4 MEV gamma rays can be generated from emissions from thoriumcontaining materials.

FIG. 1 shows an overview of an integrated process 100 for producing ahybrid fuel 120 according to one embodiment of the invention. Process100 includes a variety of sub-processes, each of which is described ingreater detail below. FIG. 1 presents an illustrative order in which thesub-processes can occur (shown by solid single lines). However, process100 is flexible, and the order of the sub-processes may be variedaccording the particular feedstocks used and hybrid fuel 120 desired. Infact, in some implementations, one or more of the sub-processes may beomitted. This aspect is represented in broken double lines. FIG. 1 alsoshows an illustrative implementation of the process 100 for producing adrop-in replacement for heating oil 118, described in more detail below(shown in solid double lines).

Process 100 includes a biofuel emulsion process 102 for producing abiofuel emulsion product (described in more detail below) and a liquidfuel process 104 for producing a liquid fuel product (described in moredetail below). Process 100 also includes a mixing process 106 in whichthe liquid fuel product is mixed with the biofuel emulsion. Process 100further includes a water/fuel mixing process 108 for creating anemulsion of water and oil based using the biofuel emulsion, the liquidfuel, and/or mixture product of the two. Process 100 still furtherincludes an oxygenates additive mixing process 110 for adding oxygenatesto any of the intermediate products produced in process 100. Process 100also includes an additive package mixing process 112 for adding variousadditive packages according to the feedstocks used and/or the hybridfuel 120 desired. The additive packages are described in more detailbelow.

As mentioned above, an illustrative implementation of process 100includes a process 114 for producing a heating oil product 118. In oneembodiment, the product of the biofuel emulsion process 102 is directlyused as the heating oil product 118. In another embodiment (not shown),approximately 5-20%, or in some embodiments about 10%, of the biofuelemulsion is blended with petroleum-based diesel to make a transportfuel. In yet another embodiment, the biofuel emulsion product is fed toadditive package mixing process 116 to produce the heating oil product118. Additive package mixing process 116 can be identical to process112; it is shown separately here for the sake of clarity ofillustration. Further still, a biofuel emulsion intermediate productfrom process 102 and a liquid fuel intermediate product from process 104can be combined in mixing process 106, then further combined with waterin process 108 before being combined with an additive package in process116 to produce the heating oil product 118. As mentioned above, process114 is merely illustrative of the flexibility of integrated process 100,and other sub-process combinations are within the scope of theinvention.

FIG. 2 is an overview of a biofuel emulsion process 200. In embodimentsof integrated process 100, process 200 can be used as the biofuelemulsion process 102. Process 200 feeds an oil 202, an emulsifier 204,and an alcohol 206 to a centrifugal compressor 208, which performs somemixing of the feeds and increases the pressure of the mixture for supplyto a reactor 210. In some implementations, the reactor 210 is asupercritical reactor, which subjects the mixture to high pressure(e.g., up to about 8000 psi). The intermediate product from the reactor210 is then fed to an expansion vessel 212. The expansion vessel dropsthe pressure of the mixture as the mixture is impinged on a plate toprovide a high degree of mixing and homogenization, and causes themixture components to be broken-up into small particles (in someembodiments on the order of hundreds of nanometers), thereby promotingthe formation of a stable emulsion.

In some alternative embodiments, fatty acid ethyl esters (FAEE) andglycerol 224 are generated as byproducts of process 200. In certainembodiments, the glycerol is further processed to glycol ethers, whichcan be added back into process 200 as additives (e.g., 218). Used asadditives, glycol ethers reduce viscosity and pour point of theresulting biofuel emulsion 222. It is theorized that the action of thesupercritical pressure from reactor 210 and rapid expansion creates ahigh shear environment that results in the formation of free radicalswhich then participate in the formation of FAEE and glycerol.Accordingly, the fuels containing FAEE and glycerol have increasedheating value. Moreover, the inclusion of hydrous ethanol in the fuelsdescribed herein allows for the existence of stable water in the productand additional water content.

The emulsified intermediate product is passed through an oxidizingreactor 214. In some implementations, an oxygen containing gas isbubbled through the emulsified intermediate product, which may,optionally, occur at elevated temperatures. In so doing, it is believedthat components in the emulsified intermediate products are oxidized(e.g., ethanol). By oxidizing at least a portion of the emulsifiedintermediate product, reactor 214 increases the flash point of the finalbiofuel emulsion 222. The oxidized intermediate product can be held in astorage vessel 216 for treatment with an additive package 218 viaadditive mixer 220 to produce the biofuel emulsion produce 222. Theadditive package addition is optional and is omitted in certainimplementations. In some embodiments, the additive package includesoxidation stabilizers to reduce the rate of rancidity of biofuelproduced from non-mineral crude oil feedstocks. As noted above, in someembodiments, the additive package also includes glycol ethers.

In some embodiments, the oil 202 used as a feedstock for process 200includes plant oils, animal fats, and/or oils produced by hydrouspyrolysis (e.g., thermal depolymerization). Thus, illustrative examplesof sources include Camelina, palm, soy, corn, rapeseed, Jatropha, andanimal fats and wastes from various livestock farming operations. Incertain embodiments, the alcohol 206 is any one of a mono-, di-, tri-,polyhydric alcohol, and/or a C1 to C4 alcohol. Meanwhile, exemplaryemulsifiers 204 include, without limitation, any one or more of thevarious types of surfactants such as nonionic, ionic or partially ionic,anionic, amphoteric, cationic and zwitterionic surfactants. For example,any of the surfactants tabulated in U.S. Pat. Pub. No. 2010/0037513,entitled Biofuel Composition and Method of Producing a Biofuel, filedSep. 18, 2009 (incorporated in its entirety by reference herein) can beused as emulsifier 204.

In one illustrative implementation of process 100, the techniquesdisclosed in U.S. Pat. Pub. No. 2009/0185963, entitled Method for MakingDiesel Fuel Additive, filed Jan. 22, 2009, (incorporated in its entiretyby reference herein) are used for process 200.

In another illustrative implementation of process 100, the techniquesdisclosed in U.S. Pat. Pub. No. 2010/0186288, entitled Method forProduction of Emulsion Fuel and Apparatus for Production of the Fuel,filed Aug. 31, 2007, (incorporated in its entirety by reference herein)are used for process 200.

In yet another illustrative implementation of process 100, thetechniques disclosed in U.S. Pat. No. 4,526,586, entitled MicroemulsionsFrom Vegetable Oil And Aqueous Alcohol With 1-Butanol Surfactant AsAlternative Fuel For Diesel Engines, filed Sep. 24, 1982, (incorporatedin its entirety by reference herein) are used for process 200.

FIG. 3A shows an overview of a process 300 for producing a liquid fuelproduct 328. In embodiments of integrated process 100, process 300 canbe used as the liquid fuel process 104. A light gas 302 and a liquidfuel feed 304 are fed via a pump and/or compressor 306 through anejector 308 to a reactor vessel 310 (as shown by solid lines).Optionally, the light gas 302 and liquid fuel feed 304 can be fed alongwith water 308 (which can be treated to have a negativeoxidation/reduction potential (ORP) in the range of about −100 eV toabout −500 eV), a catalyst 311, and/or an emulsifier 312 topump/compressor 306 (shown by double lines) via a homogenizer 313. Insome embodiments, air is also added in the process, throughpump/compressor 306. The pump/compressor 306 and/or homogenizer 313increases the homogeneity of the mixture before passing it through theejector 308. The pump/compressor 306 can include a high shearcentrifugal pump that assists in reducing the size of the droplets ofindividual components of the mixture. Moreover, the ejector 308 aids inthe production of small bubbles and/or fluid droplets (depending on thephase of the component) that increases the reactivity of the componentsof the mixture by increasing overall contact between the components.

Although not shown, all of the components that can be feed to thehomogenizer 313 can be fed directly to the pump 306 while the liquidfuel feed 304 passes through the homogenizer 313 before entering thepump 306. In such an implementation, the homogenizer breaks-up theliquid fuel feed 304 (which could include, e.g., heavy oil, bitumen,and/or other highly viscous components) into small droplets, therebyenhancing the reactivity of the liquid fuel feed 304 (by, e.g.,increasing the surface area to mass ratio). In the alternative, theliquid fuel feed 304 may be treated in a pre-processing (not shown) thatbreaks-up the liquid fuel feed as immediately described. Suitabletechniques for breaking-up the droplets of highly viscous feedstockinclude those disclosed in U.S. Pat. Pub. No. 2010/0101978, entitledFlow-Through Cavitation-Assisted Rapid Modification of Crude Oil, filedOct. 26, 2009, Canadian Pat. Pub. No. 2400188, entitled Method AndDevice For Resonance Excitation Of Fluids And Method And Device ForFractionating Hydrocarbon Liquids, filed Mar. 22, 2000, and U.S. Pat.Pub. No. 2010/0260649, entitled Deep Conversion Combining TheDemetallization And The Conversion Of Crudes, Residues Or Heavy OilsInto Light Liquids With Pure Or Impure Oxygenated Compounds, filed Jun.28, 2010 (all of which are incorporated in their entireties by referenceherein). For relatively lower viscosity liquid fuel feed 304 materials,an industrial homogenizer can be used to break-up the droplets in theliquid fuel feed 304.

The reactor vessel 310 can be a fixed-bed, fluidized-bed, moving-bed,bubble, or slurry catalytic reactor. The catalyst can be supported on azeolite and include a single transition metal or a combination oftransition metals in the form of metal salts, pure metals, and/or metalalloys. Transition metals having atomic numbers ranging from 23 to 79are preferred, and those with atomic numbers ranging from 24 to 74 aremore preferred. In addition, other non-transition metals can be used inplace of or in combination with the transition metal catalysts (e.g.,aluminum). The catalysts can be in the form of pellets, granules, wires,mesh screens, perforated plates, rods, and or strips. In oneillustrative implementation, a catalyst mixture includes aluminum wire,cobalt wire (an alloy containing approximately 50% cobalt, 10% nickel,20% chromium, 15% tungsten, 1.5% manganese, and 2.5% iron), nickel wire,tungsten wire, and cast iron granules. In another embodiment, thecatalyst is in the form of a metal alloy wire. Such metal alloy wiresinclude, without limitation, the transition metals described aboveincluding without limitation, organomolybdenum catalysts. The catalystscan be arranged in a fixed or fluid-bed arrangement in combination withgas and liquid distribution manifolds inside the vessel 310. Furthermore, wire mesh screens (constructed of catalyst materials or otherwise)can be employed within the reactor vessel 310 to promote contact betweengaseous reactants and the catalysts.

During operation, the reactor vessel 310 and its contents are maintainedat a temperature above ambient temperature and typically below theboiling or decomposition temperature of the liquid phase of the reactionmixture. The vessel 310 is heated using any of known methods for heatingreaction vessels, e.g., an internal or external inductive heater, asteam jacket, etc. The reaction is typically operated at or within twoatmospheres above ambient pressure.

In some implementations, the reactor vessel 310 includes or enables thecreation of an activating energy source for the breaking of C—C and/orC—H bonds in the methane and/or other natural gas components. Theactivating energy source may include radiation from microwave, infrared,or other sources. In one implementation, a non-thermal plasma is theactivating energy source according to the techniques set forth in U.S.Pat. No. 7,494,574, entitled Methods For Natural Gas And HeavyHydrocarbon Co-Conversion, filed Feb. 3, 2005 (incorporated in itsentirety by reference herein).

In other implementations, wires or other point source media are disposedinside the reactor vessel 310 (which may include catalyst materials)such that bubbles and/or liquids flows through the media create electricfields and voltage potentials in the liquid and gas phases in thereactor. Thus, the spacing of the wires, particles, and/or plates causesthe creation of energy for activating the methane and other reactants inbubbles in the intimate proximity of the catalyst. Utilizing theelectrostatic voltage generated by flowing bubbles and/or liquids inmultiphase turbulent flow, thus, provides the activating energy usefulif driving the reactions. In an embodiment, the techniques disclosed inTwo Phase Streaming Potentials (S. S. Marsen, Pet. Eng. Dept., StanfordUniversity; M. W. Wheatall, ARCO International) (incorporated in itsentirety by reference herein) can be scaled-up and applied to thereactor vessel 310 to achieve the desired electrostatic voltage forreactant activation.

In still other implementations, sonic energy may be used as a source ofactivating energy. This may include subsonic, ultrasonic, and or sonicenergy in the audible region.

In certain embodiments, oxygen and/or air are included in the light gas302 or is separately fed to the reactor vessel 310 (separate feed notshown). In these embodiments, the reactor vessel 310 is configured andthe reaction conditions are controlled to produce organic oxygenatesand/or synthesis gas from the oxygen and natural gas componentsaccording to the techniques set forth in Oxygen Pathways and CarbonDioxide Utilization in Methane Partial Oxidization in AmbientTemperature Electric Discharges (D. W. Larkin, T. A. Caldwell, L. L.Laban, and R. G. Mallinson; Energy & Fuels 1998, 12, 740-744) and/orPartial Oxidation of Methane with Air for Synthesis Gas Production in aMultistage Gliding Arc Discharge System (T. Sreethawong, P.Thakonpatthanakun, S. Chavadej; Chulalongkorn University; Availableonline 12 Sep. 2006) (incorporated in their entireties by referenceherein).

Gaseous product from the reaction is taken from the headspace of thereactor vessel 310 and fed through a gas phase catalytic reactor 314. Insome implementations, reactor 314 contains the same type of catalystused in reactor vessel 310. Reactor 314 aids in the completion of thereaction(s) between any un-reacted components that may have been carriedover from the headspace of vessel 314. The output of reactor 314 passesthrough heat exchanger 316, including coolant loop 318, to condense atleast part of the gaseous reaction product. The heat exchanger 316 andcoolant loop 318 are sized to condense and cool the vaporous productresulting from the reactions, as certain of the formed compounds canrevert and/or decompose rapidly in the gaseous phase and/or at elevatedtemperatures. Rapid cooling is preferred to quench products.

The condensed product and remaining vapors pass into a collection vessel320. The vapors in the headspace 322 of the collection vessel 320 arerecycled back to the reactor vessel 310 via a pump/compressor 324 andejector 326, which can be the same or similar as that described above.Meanwhile, the condensate in the collection vessel 320 comprises theliquid fuel product 328. Reaction byproducts 330 can be removed from thesystem and further separated via a separator 332. These byproducts caninclude heavy fractions, alkanes and sulfur compounds. The separator 332can include a filter, membrane, centrifuge, still, column, and/or otherknown apparatus for separating liquids and solids as well as separatingdifferent liquid fractions from one another.

In one implementation, the separator 332 is a centrifuge that separatessolid sulfur compounds from the liquid components (which can includealkanes). The solid sulfur compounds are discarded as waste 334, and atleast a portion of the liquid components 336 are passed into a mixer 338along with a portion of the liquid from the collection vessel 320. Themixer 338 can be any mixer known in the art, such as a splash mixer. Theblend produced by the mixer 338 can also be used as a liquid fuel 328.

As noted above, the light gas 302 includes, without limitation, methane,ethane, propane, butane, pentane, hydrogen, carbon dioxide, carbonmonoxide, ethylene, ethanol, methanol, or combinations thereof. In someembodiments, water is added to the light gas. In some implementations,the light gas 302 is activated by exposing the light gas 302 to a sourceof infrared radiation. In some implementations, the radiation islong-wavelength infrared (i.e., light in the 3-8 μm range) and/ormid-wavelength infrared (i.e., light in the 8-15 μm range). However, theuse of any wavelengths in the infrared range are within the scope of theinvention (e.g., 0.75-1,000 μm). Activation of the light gas is believedto increase the energy of the gas, thereby improving the reactioncharacteristics of the light gas 302. Thus, the light gas 302 is thoughtto more completely, and/or more rapidly, react with the liquid fuel feed304 and/or achieve reactions with higher molecular weight and/oraromatic compounds in the liquid fuel feed 304. In some implementation,the processes set forth in U.S. Pat. No. 7,721,719, entitled FuelActivation Apparatus for Methane Gas, filed Feb. 16, 2006, and/or U.S.Pat. Pub. No. 2009/0120416, entitled Fuel Activator Using MultipleInfrared Wavelengths, filed Nov. 13, 2007, are used to provide anactivated light gas 302 (both are incorporated in their entireties byreference herein).

The liquid fuel feed 304 can include fuels derived from fossil fuels orrenewable resources. Examples include one or blends of mineral oil,gasoline, diesel fuel, jet fuel, rocket fuel, petroleum residuum-basedfuel oils (e.g., bunker fuels and residual fuels), straight-run dieselfuel, feed-rack diesel fuel, light cycle oil. Liquid fuel feed 304 mayalso include one or blends of crude oil fractions, including productsfrom hydrocracking, catalytic cracking, thermal cracking, coking, and/ordesulfurization processes. Liquid fuel feed 304 may also comprise lightstraight-run naphtha, heavy straight-run naphtha, light steam-crackednaphtha, light thermally cracked naphtha, light catalytically crackednaphtha, heavy thermally cracked naphtha, reformed naphtha, alkylatenaphtha, kerosene, hydrotreated kerosene, atmospheric gas oil, lightvacuum gas oil, heavy vacuum gas oil, residuum, vacuum residuum, lightcoker gasoline, coker distillate, FCC (fluid catalytic cracker) cycleoil, and FCC slurry oil. In some implementations, the liquid fuel feed304 is activated by exposing the liquid fuel feed 304 to a source ofinfrared radiation, as described above for the light gas 304. The use ofinfrared radiation for material activation does not preclude the use ofshorter wavelengths to achieve activation, e.g., wavelengths in thenanometer range.

In embodiments in which the light gas 302 and/or the liquid fuel feed304 are activated by a source of infrared radiation, the source ofinfrared radiation can be included in the reactor vessel 310. In otherimplementations, the source of infrared radiation is external to thereactor vessel 310, but is upstream of the reactor vessel. For example,the source of radiation can be immediately downstream of the ejector 308and immediately upstream of the reactor vessel 310. In furtherimplementations, the source of infrared radiation is upstream of thepump 306 and can be in any of the feeds to the pump 306 (e.g., the lightgas 302 feed, the liquid fuel 304 feed, and/or the feed from thehomogenizer 313), or in any of the feeds to the homogenizer 313.

In another embodiment, the activated light gas 302 and/or liquid fuelfeed 304 are not processed in the reactor vessel 310. Rather, they aremixed after or during activation, and the liquid fuel product resultstherefrom. FIG. 3B shows an overview of an alternate process 350 formaking the liquid fuel product 328. The elements of process 350 thatshare the same reference numerals as the elements of process 300 are thesame as those described above. Possible alternative placements ofexternal sources of infrared radiation are shown as radiation source 352(these correspond to the placements described in connection with FIG.3A, but are shown on FIG. 3B for ease of illustration). In oneimplementation, the light gas 302 and/or liquid fuel 304 are activatedas set forth above (e.g., upstream of pump 306 or downstream of ejector308), mixed in pump 306, and ejected into a settling tank 354. Theliquid bottoms of settling tank 352 are the alternate liquid fuelproduct 328. In another implementation, the source of infrared radiationis in settling tank 354. In yet further embodiments, the light gas 302and liquid fuel 304, either one or both of which can be activated, cansimply be mixed and provided as the alternate liquid fuel product.

As mentioned above, it is believed that activating the light gas 302and/or the liquid fuel feed 304 causes the materials to become morereactive, thereby increasing the speed of reaction of the components. Itis hypothesized that activating the materials modifies thestereochemistry of the reactants, which permits reactions that wouldotherwise not occur to take place. In addition, it is thought thatactivating the reactants increases the effectiveness of catalysts.Further still, it is postulated that activated reactants can beemulsified without the need for an emulsifier or surfactant. Thetechniques and apparatus set forth in Photoassisted Activated of MethaneOver Supported Catalysts With a Xenon Excimer Lamp (Loviat, F., ETHZürich, 2009), Bond- and Mode-Specific Reactivity of Methane on Ni(100)(Maroni, P., École Polytechnique Fédérale De Lausanne, 2005),Infrared-Excitation for Improved Hydrocarbon Fuel's CombustionEfficiency (Wey, A., Handy, R. G., Zheng, Y., and Kim, C., SAEInternational, 2007) (all incorporated in their entireties by referenceherein) can be used to achieve the activated reactants.

In some implementations of process 300, the techniques disclosed in U.S.Pat. Pub. No. 2009/0249682, entitled Conversion of Biogas to LiquidFuels, filed Apr. 7, 2008, U.S. Pat. No. 7,806,947, entitled LiquidHydrocarbon Fuel from Methane Assisted by Spontaneously GeneratedVoltage, issued Oct. 5, 2010, and/or U.S. Pat. No. 7,897,124, entitledContinuous Process and Plant Design for Conversion of Biogas to LiquidFuel, filed Sep. 18, 2008 (all incorporated in their entireties byreference herein) can be used to provide the liquid fuel product 328.

It is proposed that under certain operating conditions, process 300enables the direct conversion of the light gas 302 to a liquid fuel inwhich certain light gases, e.g., methane, behave as a source of hydrogenfor the upgrading of various oils and liquid fuel feedstocks. Similarly,some have theorized that a relatively longer chain alkane (A) can bereacted with methane to produce two relatively shorter chain alkanes (B,C) according to Equation 1.

This “methane-olysis” catalytic reaction (Equation 1), as it issometimes called, results from bringing methane into contact with atleast one other starting alkane (A) having n carbon atoms with n beingequal to at least 2, preferably to at least 3, so that the catalyticreaction generally results in the formation of at least one final alkane(B) or of at least two final alkanes (B, C) having a number of carbonatoms ranging from 2 to (n−1) or even to a value greater than (n−1).This is because the alkane or alkanes resulting directly from themethane-olysis reaction can themselves participate in at least onereaction for the metathesis of other alkanes. The use of the word alkanedoes not preclude applicability to other fractions, e.g., aromatics,alkenes, etc.

It is known that methane can be one of the starting feedstocks forsynthetic liquid fuel generation. For example, methane and steam canreformed to create hydrogen and carbon monoxide. The hydrogen and carbonmonoxide are then reacted in a Fischer-Tropsch process to create liquidfuels. However, the capital expenditure needed for a Fischer-Tropschplant is at least an order of magnitude higher than that needed for thepresently disclosed process. Moreover, the present process is up to 30%more efficient than a Fischer-Tropsch process.

Moreover, by directly coupling methane (and/or other natural gascomponents) to hydrocarbon and/or bio-derived fractions and/or consumingthe methane in an alkane-alkane reaction, natural gas that is availablefor use (and which might otherwise be flared) is converted to a liquidfuel. In addition, process 300 reduces the aromatic hydrocarbon and,particularly, polycyclic aromatic hydrocarbon (PAH) content of the finalfuel product. PAHs in diesel and jet fuels possess a number ofundesirable properties, such as very poor ignition characteristics andcetane numbers, unfavorable cold-flow properties, a propensity for sootformation and a very low hydrogen content. This results in high specificcarbon dioxide emissions from the engine.

The maximum level of PAHs permitted in diesel fuels is regulated in manycountries, and some countries are proposing to lower those limits. Thus,certain refinery streams which contain relatively high levels of PAHs,such as light cycle oils from fluid catalytic cracking or middledistillate fractions from delayed or fluid cokers, can only be blendedinto diesel fuel in a limited amounts. The issue of PAH content in fuelswill be aggravated when significantly larger portions ofnonconventional, hydrogen poor heavy oils will be processed in thefuture, such as bitumen from oil sands or ultra-heavy oils of theOrinoco type. Selective hydrodecyclization of PAHs occurring in middledistillates into hydrogen-rich, high-value fuel components, likeone-ring naphthenes or, preferably, alkanes, without degradation of thecarbon number continues to be a major challenge of heterogeneouscatalysis. Thus, the processes set forth herein provide ways to useotherwise troublesome feedstocks to produce fuels with relative low PAHcontent.

Further still, embodiments of process 300 provide a fuel product thathas an improved viscosity and reduced cloud point relative to the rawliquid fuel feed. Process 300 also removes sulfur from the raw liquidfuel feed.

FIG. 4 shows a biofuel emulsion and liquid fuel mixing process 400. Inembodiments of integrated process 100, process 400 can be used as thebiofuel emulsion and liquid fuel mixing process 106. Process 400includes a mixer reactor 402 to which a biofuel emulsion product 404 anda liquid fuel product 406 are fed to produce a hybrid fuel product 408.The biofuel emulsion product 404 and liquid fuel product 406 can beproduced by any of the embodiments described above. Mixer reactor 402can be any type of mixer (e.g., splash blender) appropriate to thefeedstock. In process 400, the biofuel emulsion 404 is blended with theliquid fuel 406 at about 0.5% to about 20% by volume. Blending biofuelwith liquid fuel results in several beneficial properties for the hybridfuel. The addition of biofuel also improves lubricity of the fuel, alsoreduces the viscosity of the resulting hybrid fuel, and lowers the pourpoint.

FIG. 5 shows a process 500 for producing a water/fuel blend product 508(also called water-in-oil (W/O) product). In embodiments of integratedprocess 100, process 500 can be used as the water/fuel mixing process108. Process 500 includes a blending reactor 502 to which water 504, afuel product 506, and, optionally, an emulsifier 508 are fed to producea water/fuel blend 510. The fuel product 506 can be a biofuel emulsion404 and/or a liquid fuel 406, as described above. The blending reactor502 disperses the water 504 into the continuous phase of fuel 506.

In some implementations, blending reactor 502 includes an electrolyticcell, an ultrasonic wave generator and transducer, and/or a stirringdevice. In such case, the techniques and apparatus disclosed in U.S.Pat. Pub. No. 2010/0095580, entitled Emulsion Fuel, and Process AndApparatus for Production Thereof filed Jun. 15, 2007, (incorporated inits entirety by reference herein) are used to blend the water 504, thefuel product 506, and the emulsifier 508. Meanwhile, otherimplementations use the techniques and apparatus set forth in U.S. Pat.Pub. No. 2010/0122488, entitled Oil Emulsion, filed Apr. 4, 2008,(incorporated in its entirety by reference herein) to form the blend510. As discussed in that application, certain ion exchange resins andmineral substances (e.g., tourmaline and silicon dioxide) are used topre-treat the water to be used in the process. These materials andtechniques are used in embodiments of the present invention also.

In further implementations, blending reactor 502 includes amicronization device, for example, any of the commercial nanomizerproducts sold by Nanomizer, Inc. of Yokohama, Kanagawa, Japan. Thetechniques for use and further details of such apparatus are disclosedin U.S. Pat. Pub. No. 2010/0186288, entitled Method for Production ofEmulsion Fuel and Apparatus for Production of the Fuel, filed Aug. 31,2007. In addition, surfactants that are commercially available fromNanomizer, Inc. (e.g., Nanoemer GFA-001) are used in certainimplementations of process 500 for the emulsifier 508. The optionalemulsifier 508 is selected based on the fuel composition to beemulsified. Even differences of oil origination can affect performance.

In still further embodiments, blending reactor 502 is a high shearreactor configured for combining the water 504, fuel product 506, andemulsifier 508. This can be a single device or a plurality of devices inseries or in parallel. In general, a high shear reactor is a mechanicaldevice capable of producing submicron and micron-sized bubbles and/ordroplets in a reactant mixture flowing through the high shear reactor.High shear reactors mix the reactant mixture components by disruptingthe fluid and/or gas particles of the mixture. High shear reactor can beany one or more of homogenization valve systems, colloid mills, and/orhigh speed mixers.

In homogenization valve systems, fluid to be processed is pumped undervery high pressure through a narrow-gap valve into a lower pressureenvironment (as described above). The pressure gradients across thevalve and the resulting turbulence and cavitation act to break-up anyparticles in the fluid. High speed mixers usually have paddles, rotors,and/or blades that turn at high speed in a fluid, thereby producingaverage particle sizes of greater than 20 microns.

Meanwhile, a typical colloid mill configuration includes a conical ordisk rotor that is separated from a complementary, liquid-cooled statorby a closely-controlled rotor-stator gap. Rotors are usually driven byan electric motor through a direct drive or belt mechanism. As the rotorrotates at high rates, it pumps fluid between the outer surface of therotor and the inner surface of the stator, and shear forces generated inthe gap process the fluid. Many colloid mills with proper adjustmentachieve average particle sizes of 0.1-25 microns in the processed fluid.These capabilities render colloid mills appropriate for a variety ofapplications including colloid and oil/water-based emulsion processing.

As stated above, blending reactor 502 disperses the water 504 into thefuel product 506, which is typically the continuous phase. Suitablecolloidal mills are manufactured by IKA® Works, Inc. Wilmington, N.C.and APV North America, Inc. Wilmington, Mass., for example. In someimplementations, the blending reactor 502 includes the Dispax Reactor®of IKA® Works, Inc. U.S. Pat. Pub. No. 2009/0001316, entitled System andProcess for Production of Liquid Product from Light Gas, filed Jun. 17,2008, (incorporated in its entirety by reference herein) disclosessystems and techniques for the use of high shear devices. Any of thesetechniques and/or systems can be used as a high shear reactor and or anyother high shear mixing device disclosed herein.

The stability of the blend 510 depends, at least in part, on theparticle size of water 504. The particle size of the water isdetermined, in part, by the ORP of the water. The goal is to createwater droplet size in the blend 508 of 1-5 μm. In some implementations,water 504 is treated to have a negative ORP in the range of about −100eV to about −500 eV. Water/fuel blends (i.e., emulsions) containingnegative ORP water are believed to exhibit excellent efficiencyimprovements (exceeding 30% increase) over the fuel alone.

Blends of the type described herein have demonstrated significantadvantages in engine and heating applications and are believed to resultin reduced Greenhouse Gas (GHG), carbon dioxide, hydrocarbon, and NO_(x)emissions.

FIG. 6 shows a process 600 for combining a liquid fuel 602 and anoxygenate additive 604 in a mixer reactor 606. The liquid fuel 602 canbe any of the liquid fuels described herein, including anyimplementation of the biofuel emulsions described above. Process 600also includes a mixer reactor 608 for blending an additive package 610to produce a hybrid fuel 612. Mixer reactors 606 and 608 can be anymixer known to those skilled in the art, and can include any variety ofsplash mixer. Mixed reactors 606 and 608 can be a single mixer. As shownin FIG. 6, the process 600 can include the blending of oxygenateadditives 604 and other additive packages 610 (as shown in solid lines),or either additive can be omitted (shown in broken double lines).

In some implementations, the oxygenate additive 604 can includecommercially available oxygenate additive, such as methyl tert-butylether (MBTE), tertiary amyl methyl ether (TAME) ethanol, and others. Inother implementations, the biofuel emulsion 222 is used as the liquidfuel 602, in which a blended alcohol serves the purpose of an oxygenateadditive, and no further oxygenate is needed. In still furtherimplementations, oxygen and/or carbon dioxide are included in light gas302 during the manufacture of the liquid fuel product 328, and nofurther oxygenate is needed. In such an embodiment, the techniquesdisclosed in U.S. Pat. Pub. No. 2005/0288541, entitled Gas to LiquidConversion Process, filed Dec. 2, 2004 (incorporated in its entirety byreference herein), can be used to oxygenate the liquid fuel product 328.

In some implementations, the additive package 610 can include any one ormore of the following additives: an additive to increase oxidationstability, an additive to adjust viscosity, a rust inhibitor, anadditive to adjust lubricity, and/or an additive to enhance a fuel'scetane number. In some embodiments, the additive is a glycol ether. Insome embodiments, the additive has the effect of reducing the pour pointof the hybrid fuel 612. Specific examples of additives include thefollowing: dimethyl ether (DME), anti-wear additives as disclosed inU.S. Pat. No. 4,185,594, and commercially available cetane boosters.

Referring to FIG. 1, as mentioned above, process 100 is a flexibleprocess, and the above-described sub-processes can be varied or omitteddepending on the availability of certain feedstock and/or the desiredproduct. For example, in one embodiment of process 100, a biofuelemulsion from process 102 is reacted with natural gas in process 300. Inso doing, it is believed that aromatic hydrocarbons present in thebiofuel emulsion are cracked or otherwise transformed into nonaromaticcompounds, which enables a more efficient and cleaner-burning fuelrelative to the biofuel emulsion alone.

FIG. 7 shows a process 700 for producing hybrid fuel feedstocks fromheavy oils. As explained above, one aspect of the invention is that theoverall process 100 is flexible and can be fully integrated with avariety of processes for oil production, oil refining, fuel production,and/or chemical manufacturing. Process 700 provides an illustrativeexample of one possible implementation of an integration of process 100with a process for the conversion into liquids (gasolines, gas oil,fuels) of hydrocarbons that are solid or have a high boilingtemperature, laden with metals, sulfur, sediments, with the help ofwater or oxygenated gas, shown generally as process 702. Process 702 isdescribed in detail in U.S. Pat. Pub. No. 2010/0260649. As explainedtherein, the process 702 comprises preheating a feed 5 in a heater 8 toa temperature below the selected temperature of a reactor 10. This feedis injected by injectors 4 into the empty reactor 10 (i.e., withoutcatalyst.) The feed is treated with a jet of gas or superheated steamfrom superheater 2 to activate the feed. The jet of gas may be, forexample, from gas 704, which can include carbon dioxide. The activatedproducts in the feed are allowed to stabilize at the selectedtemperature and at a selected pressure in the reactor and are then runthrough a series of extractors 13 to separate heavy and lighthydrocarbons and to demetallize the feed. Useful products appearing inthe form of water/hydrocarbon emulsions are generally demulsified inemulsion breaker 16 to form water laden with different impurities. Thelight phase containing the final hydrocarbons is heated in heater 98 andis separated into cuts of conventional products, according to the demandfor refining by an extractor 18 similar to 13.

Heavy fractions 708 from extractor 18 can be recycled to the process ascrude feed 5. In addition, heavy fraction 708 can be used as liquid fuelfeed 304 in process 300. Moreover, other heavy oil 710 and/or a liquidfuel product 712, such as any described above, can be supplied as crudefeed 5. Thus, in this way, intermediate and/or final products fromprocess 100 can be integrated as feed for process 702.

In addition to integrating materials produced by process 100 intoprocess 702, embodiments of the invention integrate materials producedby process 702 into process 100. For example, a light gas product 714can be produced as a product from the extractors 13. The light gasproduct 714 can be used as the light gas feedstock (e.g., light gas 302of process 300) for any of the liquid fuel processes described herein.Similarly, an oxygenated fuel 716 can be produced as a product from theextractors 13. In some implementations, the oxygenated fuel 716 can beintegrated into process 100 in substitution for the biofuel emulsion102. Similarly, in some implementations, a liquid diesel fuel 718 can beused as a liquid fuel feed 304 in process 300.

FIG. 8 shows a process 800 for producing feedstocks from carbonaceousmaterials for use in the hybrid fuel processes disclosed herein. Inprocess 800, a carbonaceous feedstock 802, such as coal, biomass and/orpetroleum coke, a catalyst 804, such as an alkali metal, and steam 806,is supplied to a hydromethanation reactor 808. Reactor 808 produces aplurality of gases, including methane, by the reaction of the feedstockin the presence of the catalyst and steam at elevated temperatures andpressures. Fine unreacted carbonaceous materials are removed from theraw gas product by, e.g., a cyclone 810 and the gases are cooled andscrubbed in multiple processes 810, 812 to remove undesirablecontaminants and other side-products 814 including carbon monoxide,hydrogen, carbon dioxide and hydrogen sulfide, to produce a light gasstream 816, which includes methane. Exemplary carbonaceous feedstockmaterials, include without limitation cellulosic feedstock (i.e., woodchips).

The hydromethanation of a carbonaceous materials to methane typicallyinvolves four separate reactions:Steam carbon: C+H₂O→CO+H₂Water-gas shift: CO+H₂O→H₂—+CO₂CO Methanation: CO+3H₂→CH₄+H₂OHydro-gasification: 2H₂+C→CH₄

In the hydromethanation reaction, the result is a “direct”methane-enriched raw product gas stream, which can be subsequentlypurified and further methane-enriched to provide the final light gasproduct 816. This is distinct from conventional gasification processes,such as those based on partial combustion/oxidation of a carbon source,where a syngas (carbon monoxide+hydrogen) is the primary product (littleor no methane is directly produced), which can then be further processedto produce methane (via catalytic methanation, see reaction) or anynumber of other higher hydrocarbon products. When methane is the desiredend-product, the hydromethanation reaction provides the possibility forincreased efficiency and lower methane cost than traditionalgasification processes. In some implementations, the techniquesdisclosed in U.S. Pat. Pub. No. 2010/0292350, entitled Processes forHydromethanation of a Carbonaceous Feedstock, filed May 12, 2010,(incorporated in its entirety by reference herein) are employed asprocess 800.

Process 800 can be integrated with processes 300 and 700 such that thelight gas 816 produced by process 800 can be the light gas 302.Similarly, the carbon dioxide from side-products 814 can be the gas 704used by process 700. Likewise, the heavy fractions 708 from process 700can be the carbonaceous feedstock 802 for process 800.

FIGS. 9A-9D depict different embodiments of the non-thermal plasmareactors described herein. In these embodiments, syngas is generated vianon-thermal plasma techniques. Radicals produced from the production ofsyngas are utilized directly in subsequent reactions with oil. Incertain embodiments, the non-thermal plasma is gliding arc plasma.Gliding arc plasma uses dynamic discharge to create the plasma while thecorona discharge generates the plasma with a static discharge. Incertain embodiments, the gliding arc has two diverging electrodes. Anarc is formed where the gas enters by applying a high voltage. The gaspushes the arc down the length of the reactor. As the gas reaches theend of the reactor, the arc is turned off. Another arc is then formed atthe gas entrance.

FIG. 9A shows an apparatus 900 for producing a liquid fuel product, inparticular for producing a hybrid fuel. In the embodiment depicted,apparatus 900 is a gliding arc reactor, which is a specific embodimentof a non-thermal plasma reactor. In the embodiment depicted in FIG. 9A,liquid and gas are co-processes through the reactor. The plasma isacting simultaneously on the liquid and the gas. In embodiments ofintegrated process 100, apparatus 900 can be used to produce the lightgas/liquid fuel process 104. Similarly, in the embodiments of process300, apparatus 900 can be used for reactor vessel 310, including, insome embodiments, pump/compressor 306 and ejector 308. Similarly, inprocess 350, the apparatus 900 can be used for activation source 352.

Apparatus 900 includes an inlet 901 for introduction of a light gas,liquid fuel (e.g., alcohol or oil), or mixture thereof. Apparatus 900further includes electrodes 903 and high voltage connectors 908. Highvoltage connectors 908 are connected to an electricity source and supplyvoltage to electrodes 903. In some embodiments, high voltage connectorssupply a pulse up to about 90 kV, corresponding to about 20 KW DC to 30kHz. Electrodes 903 are in fluid communication with inlet 901 (in someembodiments along the path defined by prechamber 911). In certainembodiments, electrodes 903 are low work force cathodes (i.e., made fromlow work force metals). Exemplary low work force cathodes include,without limitation, thorium. Upon application of voltage from highvoltage connectors 908, an electric discharger, or arc, 904 is formedwhich travels along the length of the electrodes. Apparatus 900 furtherincludes an exit zone 905, which in fluid communication with the pathdefined by the electrodes. In some embodiments, exit zone 905 optionallyincludes and is in fluid communication with Helmholz coils 906, heatingcoils 912 and a catalyst bracket 913. An outlet 910 for heaving oil isalso in fluid communication with exit zone 905. A second inlet 902 isprovided and is in fluid communication with exit zone 905, such thatexit zone 905 is interposed between electrodes 903 and second inlet 902.Apparatus 900 further includes outlet 907. In some embodiments,condenser 909 is configured to collect outgoing fuel oil from theapparatus.

Upon being introduced to apparatus 900 though first inlet 901, liquidfuel travels along the path defined by electrodes 903 and, optionally,prechamber 903. Upon exposure to electrical arc 904, free radicals areformed. Electrical arc 904 pushes the liquid fuel and free radicalreaction products along the path defined by electrodes 903 to exit zone905. In exit zone 905, the free radicals are in intimate contact withliquid introduced to apparatus 900 through second inlet 902, therebyproducing a liquid fuel product. In some embodiments, the liquidintroduced through second inlet 902 is a recycled liquid, such asrecycled oil. In some embodiments, the mixture of the free radicals andthe liquid introduced through second inlet 902 is in further contactwith catalyst 913. Catalysts useful to be included in apparatus 900include those described herein. In some embodiments, heating coils 912provide for heating of the reaction mixture, while in some embodiments,Helmholtz coils 906 generate a magnetic field conducive to promoting theprocess of forming liquid fuel. The hybrid fuel formed by apparatus 900is removed from the apparatus through outlet 907. Upon exiting apparatus900, the resulting hybrid fuel is capable of further processing asdefined in integrated process 100.

The configuration of apparatus 900 allows for a process in which theliquid introduced through second inlet 902 is directly in intimatecontact with free radicals generated through the exposure of liquid fuelto the electrodes, as the free radicals are being formed. The intimatecontact afforded by the configuration of apparatus 900 provides for theimmediate combination of the two reactants, without the need forapplication of additional energy, as in conventional fuel processes.Moreover, it has been found that the hybrid fuel produced from apparatus900 demonstrates reduced viscosity and increased volume, as well as alower fraction of polyaromatic compounds.

FIG. 9B shows an apparatus 920 for producing a liquid fuel product, inparticular for producing a hybrid fuel. In the embodiment depicted,apparatus 920 is another embodiment of a gliding arc reactor, which is aspecific embodiment of a non-thermal plasma reactor. In the embodimentdepicted in FIG. 9B, the liquid reacts with syngas and radicals, whileelectron react with liquids in a catalytic contained chamber. As withapparatus 900, in embodiments of integrated process 100, apparatus 920can be used to produce the light gas/liquid fuel process 104. Similarly,in the embodiments of process 300, apparatus 920 can be used for reactorvessel 310, including, in some embodiments, pump/compressor 306 andejector 308. Similarly, in process 350, the apparatus 920 can be usedfor activation source 352.

Apparatus 920 includes many of the same features of apparatus 900,including electrodes 903, which upon application of voltage through highvoltage connectors 908, creates arc 904. Similarly, apparatus 920includes exit zone 905 which is optionally in fluid communication withcatalyst 913, Helmholtz coils 906, and heating coils 912. Apparatus 920also includes outlet 907 and condenser 909.

Apparatus 920 includes inlet 921. Inlet 921 of apparatus 920 providesfor input of light gas. In contrast, inlet 901 of apparatus 900 (seeFIG. 9A) provided for input of a mixture of gas and liquid, allowing forcoprocessing of liquid and gas through the electrodes of the gliding arcreactor. In apparatus 920, liquid in the form of oil or recycle oil isintroduced through second inlets 922 a and 922 b. In certainembodiments, recycled oil is introduced through input 922 a, while inputoil is introduced through input 922 b. In some embodiments, a solublecatalyst is also introduced through input 922 b. Inlets 922 a and 922 bare in fluid communication with exit zone 905 such that they areavailable for intimate contact with the products of the gliding arcreactor. For example, in certain embodiments, the liquid reacts withsyngas and radicals formed by the non-thermal plasma reactor, whileelectrons react with liquids in exit zone 905. In certain embodiments,exit zone 905 is a catalytic contained chamber. As with apparatus 920,after the reaction products are mixed to form a liquid fuel product, thehybrid fuel is removed through outlet 907.

FIG. 9C shows apparatus 940 for producing a liquid fuel product, inparticular for producing a hybrid fuel. In the embodiment depicted,apparatus 940 is another embodiment of a gliding arc reactor, which is aspecific embodiment of a non-thermal plasma reactor. In the embodimentdepicted in FIG. 9C, the syngas and radicals and electrons produced bythe gliding arc impinge into a flowing stream of liquid optionallycontaining a catalyst bed. As with apparatus 900 and 920, in embodimentsof integrated process 100, apparatus 940 can be used to produce thelight gas/liquid fuel process 104. Similarly, in the embodiments ofprocess 300, apparatus 940 can be used for reactor vessel 310,including, in some embodiments, pump/compressor 306 and ejector 308.Similarly, in process 350, the apparatus 940 can be used for activationsource 352.

Apparatus 940 includes many of the same features of apparatus 900 and920, including electrodes 903, which upon application of voltage throughhigh voltage connectors 908, creates arc 904. In the embodiment ofapparatus 940, exit zone 905 is optionally in fluid communication withcatalyst bed 913, Helmholtz coils 906, and heating coils 912.

Apparatus 940 includes inlet 941. Inlet 941 of apparatus 940 providesfor input of light gas. In apparatus 940, liquid in the form of oil orrecycle oil is introduced through second inlet 942. Inlet 942 is influid communication with exit zone 905 such that the reaction productsfrom the gliding arc reactor directly impinge the flowing stream ofliquid introduced through inlet 942, thereby being in intimate contactwith the products of the gliding arc reactor. After the reactionproducts are mixed to form a liquid fuel product, the hybrid fuel isremoved via outlet 907 through separator 909. In some embodiments,separator 909 is also a condenser. In apparatus 940, heavy and light oilexit the system as provided through separator 909.

FIG. 9D shows an apparatus 960 for producing a liquid fuel product, inparticular for producing a hybrid fuel. In the embodiment depicted,apparatus 960 is a gliding arc reactor, which is a specific embodimentof a non-thermal plasma reactor. In the embodiment depicted in FIG. 9D,the non-thermal plasma reactor is configured as a ‘plate’ of multiplemicroplasma reactors. The output of the plate reactors of apparatus 960impinge on liquid droplets or thin films. In embodiments of integratedprocess 100, apparatus 960 can be used to produce the light gas/liquidfuel process 104. Similarly, in the embodiments of process 300,apparatus 960 can be used for reactor vessel 310, including, in someembodiments, pump/compressor 306 and ejector 308. Similarly, in process350, the apparatus 960 can be used for activation source 352.

Apparatus 960 includes an inlet 961 for introduction of light gas intolight gas chamber 961 a. Apparatus 960 further includes ceramic plate963, which contains holes 964 through which the gas is dispersed to exitzone 965. Wires 968 are deposited on ceramic plate 963 and are inelectrical connection with a power supply 966 for application of voltage(e.g., a 6-1000V pulse). As the gas crosses ceramic plate 963, theapplied voltage creates a plurality of arcs in each of holes 964,thereby providing for a reaction with the light gas and causing theformation of free radicals, which are transported into exit zone 965.

Apparatus 960 further includes a second inlet 962 for input of liquidinto liquid chamber 962 a. In some embodiments; the liquid that isintroduced through second inlet 962 is an oil or mixtures of oil. Insome embodiments, the liquid introduced through second inlet 962 is arecycled liquid, such as recycled oil. The liquid is transported acrossdiffuser plate 969 to exit zone 965. Upon introduction to exit zone 965,the diffused liquid comes into intimate contact with the reactionproducts of the light gas that has been transported through ceramicplate 963, thereby producing a hybrid electric fuel product. Optionally,catalyst bed 973 is present in exit zone 965. Also, optional heaters 972heat apparatus 960. After the reaction products are mixed, they exit theapparatus through outlet 967. In some embodiments, an optional vacuumpump is located between exit zone 965 and outlet 967. Upon exitingapparatus 960, the resulting hybrid fuel is capable of furtherprocessing as defined in integrated process 100.

In FIGS. 9A-9D, the configuration of each apparatus 900, 920, 940, and960 provides for a process in which the liquid is directly in intimatecontact with free radicals generated through the exposure of liquid fuelto the electrodes, as the free radicals are being formed. The intimatecontact afforded by the configuration of each apparatus provides for theimmediate combination of the reactants, without the need for applicationof additional energy, as in conventional fuel processes. Moreover, ithas been found that the hybrid fuel produced from apparatus 900, 920,940 and 960 demonstrates reduced viscosity and increased volume, as wellas a lower fraction of polyaromatic and aromatic compounds.

The hybrid fuels 120 produced by embodiments of process 100 possesssuperior performance characteristics relative to competing fuels (e.g.,biodiesel fuels, “green diesel” fuels, straight vegetable oil fuels,oil/water emulsion fuels, and conventional petroleum fuels). Forexample, some embodiments of the hybrid fuels can be a drop-in fuelrather than having to be blended with conventional fuels. Certain hybridfuels have relatively low pour and cloud points, can withstand multiplefreeze/thaw cycles, and have relatively long term stability (e.g.,greater than 1 year). Thus, certain hybrid fuels disclosed herein aresuitable for use in cold weather. In one illustrative example, a hybridfuel comprising about 20% by volume Next Generation Diesel (commerciallyavailable from Global Energy Resources, LLC of Fort Wayne, Ind.) andabout 80% by volume GDIESEL™ (commercially available from AdvancedRefining Concepts of Reno, Nev.) surprisingly exhibits about a 25° F.(14° C.) reduction in pour point relative to the individual fuelcomponents. This same hybrid fuel also surprisingly exhibits about a 5°F. (3° C.) reduction in cloud point. Accordingly, according to certainembodiments, the hybrid fuel blends disclosed herein include up to about20% of a biofuel emulsion (e.g., the result of process 102 of FIG. 1 or222 of FIG. 2). In some embodiments, the hybrid fuel blends disclosedherein include from about 5% to about 10% of a biofuel emulsion.Moreover, in some embodiments, up to about 20% water is present in thehybrid fuel.

A further proposed embodiment of a hybrid fuel includes combiningactivated natural gas and/or hydrogen with the Next Generation Dieselusing process 350 described above. It is thought that such a hybrid fuelwould exhibit lower CO2 emissions than the Next Generation Diesel alonedue to an increase in the hydrogen to carbon ratio of the fuel.

In certain embodiments of the hybrid fuels disclosed herein, thelubricity and/or viscosity of the liquid fuel is increased by theaddition of the biofuel emulsion. Thus, ultra-low-sulfur diesel (ULSD)can be used as the liquid fuel in certain formulations without sufferingthe disadvantage of the low lubricity and/or low viscosity of the ULSD.Also, the need for an additive to increase lubricity is lessened oravoided along with the increased cost and process complexity of doingso. In some embodiments, the formulations containing ULSD have lowerviscosity and pour point than either conventionally hydrotreated ULSD orbiofuel emulsion.

Further advantages include that certain hybrid fuels disclosed hereinhave reduced greenhouse gas emissions, reduced particulate emissions,and have feedstocks comprising materials produced by the consumption ofcarbon dioxide (e.g., plant oils). Total reduction in emission isexpected to be about 50% for certain processes to produce the hybridfuels. Meanwhile, a reduction of 30% in carbon dioxide and particulateemissions from end use are expected. Thus, the use of such hybrid fuelshas a reduced environmental impact. Further still, certain embodimentsof the hybrid fuels avoid the transesterification step found in manybiodiesel products. Thus, these hybrid fuels will not contain glycerin,fatty acid methyl esters (FAMEs) or fatty acid ethyl esters (FAEEs),which are usually found in at least small amounts in typical biodieselproducts. Because regulatory guidelines prohibit the presence of thesebyproducts in certain fuels (such as jet fuels), these hybrid fuels aresuitable for transportation via existing pipeline infrastructure, unlikemost common biodiesel products. Moreover, by avoiding thetransesterification process, the capital cost, operating cost,complexity, and time involved in that process are avoided. This reducesthe cost of producing such hybrid fuels.

The above-described advantages show that embodiments of the inventionprovide for drop-in fuels that meet ASTM and EU-wide targets on biofuelsand greenhouse gas emissions based on Well-to-Wheel considerations andLife Cycle Analysis. Embodiments of the hybrid fuels are considereddrop-in in that they can be used as an entire fuel rather than merely asa fuel additive. Because certain liquid hybrid fuels are formed throughthe use of natural gas, the need for liquid petroleum is reduced. Inaddition, the processes for the formation of liquid fuels can be adaptedto remote locations that presently have natural gas supply that is notbeing used.

Embodiments of the hybrid fuels formed by implementations of theprocesses described herein exhibit the desirable characteristicsdescribed above while retaining characteristics found in conventionalfuels. For example, the hybrid fuels described herein have high energycontent per pound/gallon, are able to withstand multiple freeze cycles,are stable, have favorable viscosity and cetane values (for diesel-typefuel replacements), equivalent phosphorous content, compatibledistillation curves, favorable corrosion characteristics, andcompatibility with existing seal materials.

Other illustrative embodiments can be described as follows:

Certain illustrative embodiments can involve the combining of freeradicals generated from non-thermal/non-equilibrium plasma using pureoxygen and/or other select gases (and/or separately or in combinationreforming of methane with oxygen, CO, CO2, water, hydrogen, hydrocarbongases and combinations/selected blend ratios thereof) to performreforming, cracking, hydrogenation, methylation, oxidativedesulfurization, hydrogen desulfurization, carbonylation,hydroforylation, alkylation, polymerization, and other refinery and/orchemical feedstock processes. Feedstocks and/or select plasma gasses mayalso include inert gas such as argon, zeon, nitrogen, or gas phasecomponents such as CO, Ethane, Butane, DME, Ammonia, Urea, Syngas, etc.Utilization of specific plasma intensity to provide designer reactionscan be utilized. The gas phase reactions may result in disassociation offeed gas and/or stimulation of the gases to vibrational/and/orrotational excited levels. Selecting space velocity can be utilized toachieve desired products.

Certain illustrative embodiments can involve selecting the blends ofradicals generated by non-thermal/non-equilibrium plasmas and variousgasses and the sequential and/or coprocessor treatment of selected oilfractions to achieve desired end hydrocarbon products.

Certain illustrative embodiments can involve utilization of oxygenradicals and/or stimulated fractions generated bynon-thermal/non-equilibrium plasmas for fragmentation andfunctionalization of oil streams, including:

a. Breaking up long chain molecules

b. Oxidative Desulfurization and Hydrogen Desulfurization—heavy oils andalso polishing

c. Creation of synthetic oil fractions to combine with diesel and otherproducts to increase oxygen content for better fuel performance

Certain illustrative embodiments can involve sequentially applying thetechnologies to achieve desired end products.

Certain illustrative embodiments can involve applying the technologiesto processing upstream (well head), mid-stream (refining) and at end useengine applications.

Certain illustrative embodiments can involve combining natural gasand/or oxygen with fuels to expand fuel volume and improve fuelcharacteristics.

The desirability of the oxygen containing fractions is describedpreviously herein. Certain illustrative embodiments can involveexpanding the technology for oxygen addition with plasma/free radical.Similarly, the concepts we included for heavy oil are describedpreviously herein, and certain illustrative embodiments can involve theuse of oxygen plasma and hydrogen/methane radical reactions toaccomplish goals. Certain illustrative embodiments can also involve theoxidative desulfurization technology using plasma generated freeradicals combined with HDS. By reference the application applies tobiofuels.

It will be appreciated that the scope of the present invention is notlimited to the above-described embodiments, but rather will encompassmodifications of and improvements to what has been described. Allreferences described above are incorporated in their entireties byreference herein.

What is claimed is:
 1. A hybrid fuel prepared from a process that comprises: introducing a first reactant to a reactor, wherein the first reactant comprises one or more light gases; exposing the first reactant to non-thermal plasma under conditions sufficient to reform the first reactant to form reaction products comprising at least one of syngas, free radicals, and energetic electrons; introducing a first liquid feed fuel to the reactor; and intimately contacting the reaction products from the exposure of the first reactant to non-thermal plasma with the first liquid feed fuel in the reactor to produce a modified liquid fuel that is different than the first liquid feed fuel.
 2. The hybrid fuel of claim 1, wherein the modified liquid fuel comprises hydrocarbon chains larger in size and mass than the first liquid feed fuel.
 3. The hybrid fuel of claim 2, wherein the modified liquid fuel comprises hydrocarbon chains of lengths within a given range based on the characteristics of the first liquid feed fuel used.
 4. The hybrid fuel of claim 1, wherein the process further comprises providing a catalyst.
 5. The hybrid fuel of claim 1, wherein the process further comprises adding at least one of water and air.
 6. The hybrid fuel of claim 1, wherein the process further comprises forming FAEE and glycerol as byproducts.
 7. The hybrid fuel of claim 1, wherein the reaction products include any of oxygen, hydrogen, and carbon radicals or a combination thereof.
 8. The hybrid fuel of claim 7, wherein the process further comprises breaking up long chain molecules of the first liquid feed fuel with the oxygen radicals.
 9. The hybrid fuel of claim 7, wherein the process further comprises desulfurizing the liquid feed fuel with the oxygen radicals.
 10. The hybrid fuel of claim 7, wherein the process further comprises creating synthetic liquid fuel fractions with the oxygen radicals.
 11. The hybrid fuel of claim 1, wherein the modified liquid fuel has fewer polyaromatic compounds than the first liquid feed fuel.
 12. The hybrid fuel of claim 1, wherein the modified liquid fuel has a lower viscosity than the first liquid feed fuel.
 13. The hybrid fuel of claim 1, wherein the reactor is a gliding arc reactor producing one or more arcs, a DBD, or a microplasma reactor.
 14. The hybrid fuel of claim 13, wherein the process further comprises within the gliding arc reactor, pushing the one or more arcs with the first reactant toward the liquid feed fuel.
 15. The hybrid fuel of claim 1, wherein the process further comprises producing the first liquid fuel product and a second liquid fuel product.
 16. The hybrid fuel of claim 1, wherein the first reactant further comprises one or more liquid feed fuels.
 17. A hybrid fuel prepared from a process that comprises: introducing a first reactant to a reactor, wherein the first reactant comprises one or more light gases; exposing the first reactant to non-thermal plasma under a selective condition sufficient to reform the first reactant to form reactions products containing at least one of syngas, free radicals, and energetic electrons based on the selective condition; introducing a first liquid feed fuel to the reactor; and intimately contacting the reaction products with the first liquid feed fuel in the reactor to produce a modified liquid fuel.
 18. The hybrid fuel of claim 17, wherein the selective condition comprises facilitating a vibrational excitation level of the first reactant.
 19. The hybrid fuel of claim 17, wherein the selective condition comprises facilitating a rotational excitation level of the first reactant.
 20. The hybrid fuel of claim 17, wherein the selective condition comprises facilitating the hybrid fuel to have a space velocity of the first reactant.
 21. The hybrid fuel of claim 17, wherein the reaction products include any of oxygen, carbon, and hydrogen radicals or a combination thereof.
 22. The hybrid fuel of claim 21, wherein the process further comprises breaking up long chain molecules of the first liquid feed fuel with the oxygen radicals.
 23. The hybrid fuel of claim 21, wherein the process further comprises desulfurizing the liquid feed fuel with the oxygen radicals.
 24. The hybrid fuel of claim 21, wherein the process further comprises creating synthetic liquid fuel fractions with the oxygen radicals.
 25. The hybrid fuel of claim 17, wherein the modified liquid fuel has fewer polyaromatic compounds than the first liquid feed fuel.
 26. The hybrid fuel of claim 17, wherein the modified liquid fuel has a lower viscosity than the first liquid feed fuel.
 27. The hybrid fuel of claim 17, wherein the process further comprises providing a catalyst.
 28. The hybrid fuel of claim 17, wherein the process further comprises adding at least one of water and air to perform reformation.
 29. The hybrid fuel of claim 17, wherein the reactor is a gliding arc reactor producing one or more arcs, a DBD, or a microplasma reactor.
 30. The hybrid fuel of claim 29, wherein the process further comprises, within the gliding arc reactor, pushing the one or more arcs with the first reactant toward the liquid feed fuel.
 31. The hybrid fuel of claim 17, wherein the modified liquid fuel comprises hydrocarbon chains larger in size and mass than the first liquid feed fuel.
 32. The hybrid fuel of claim 17, wherein the modified liquid fuel comprises hydrocarbon chains of lengths within a given range based on the characteristics of the first liquid feed fuel used.
 33. The hybrid fuel of claim 17, wherein the process further comprises forming FAEE and glycerol as byproducts. 